CN109569581B - Three-dimensional composite material Bi responding to visible light2MoO6/ZnO and preparation method and application thereof - Google Patents
Three-dimensional composite material Bi responding to visible light2MoO6/ZnO and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011165 3D composite Substances 0.000 title claims abstract description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 166
- 239000011787 zinc oxide Substances 0.000 claims abstract description 83
- 229910002900 Bi2MoO6 Inorganic materials 0.000 claims abstract description 38
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- 239000000243 solution Substances 0.000 claims description 32
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
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- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical group O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 claims description 4
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical group O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 3
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical group [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 27
- 239000011941 photocatalyst Substances 0.000 abstract description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 6
- 239000002114 nanocomposite Substances 0.000 abstract description 4
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- 239000002131 composite material Substances 0.000 description 25
- 239000003054 catalyst Substances 0.000 description 13
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- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
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- 238000000034 method Methods 0.000 description 6
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 5
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- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000011684 sodium molybdate Substances 0.000 description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 5
- 238000000527 sonication Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
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- 238000007146 photocatalysis Methods 0.000 description 3
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- 239000004065 semiconductor Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The inventionDiscloses a three-dimensional composite material Bi responding to visible light2MoO6The preparation method comprises the steps of preparing a one-dimensional zinc oxide nanorod by taking water-soluble zinc salt as a raw material through a hydrothermal reaction in the presence of an alkali solution and a hydrazine monohydrate solution; adding one-dimensional zinc oxide nano-rod into a solution containing bismuth salt and molybdenum salt, and preparing a visible light response three-dimensional composite material Bi through solvothermal reaction2MoO6and/ZnO. Two-dimensional Bi2MoO6The nano-sheet photocatalyst is modified on a one-dimensional ZnO nano-rod in a solvothermal mode, so that three-dimensional Bi is obtained2MoO6the/ZnO nano composite material is used for carrying out photocatalytic degradation on heavy metal wastewater so as to effectively treat the heavy metal wastewater.
Description
Technical Field
The invention belongs to the technical field of inorganic functional materials, and particularly relates to three-dimensional Bi2MoO6A preparation method of a/ZnO composite catalyst and application thereof in catalyzing and removing heavy metal wastewater.
Background
With the rapid development of industry, heavy metal wastewater discharged by the industry is increasingly polluted. Research researches have shown that heavy metals in water have strong carcinogenicity to most organisms and have high solubility in water. Seriously threatens the life health safety and the natural ecosystem of human beings. Therefore, the method for degrading and removing the heavy metal wastewater by using a cheap, efficient and energy-saving method becomes a hot problem of environmental research. At present, the semiconductor photocatalysis technology has the advantages of no toxicity, high degradation efficiency, strong oxidation-reduction capability and the like, and is considered to be one of the most economic and effective methods for degrading and removing the pollution of various heavy metal wastewater. Among the many photocatalysts in use, ZnO is an oxide semiconductor photocatalyst which has been widely studied, however, ZnO also has its own deficiency such as a forbidden band width of 3.2eV, and thus its photoresponsiveness to the visible light region and the near infrared region is almost zero.
Disclosure of Invention
The invention aims to introduce and provide a three-dimensional composite material Bi capable of responding to visible light2MoO6/ZnO, preparation method thereof and heavy metalVisible light catalytic degradation of wastewater. Two-dimensional Bi2MoO6The nano-sheet photocatalyst is modified on a one-dimensional ZnO nano-rod in a solvothermal mode, so that three-dimensional Bi is obtained2MoO6The invention relates to a ZnO nano composite material, which can be used for carrying out photocatalytic degradation on heavy metal wastewater to effectively treat the heavy metal wastewater.
In order to achieve the purpose, the specific technical scheme of the invention is as follows:
three-dimensional composite material Bi responding to visible light2MoO6The preparation method of ZnO comprises the following steps:
(1) taking water-soluble zinc salt as a raw material, and preparing a one-dimensional zinc oxide nanorod by a hydrothermal reaction in the presence of an alkali liquor and a hydrazine monohydrate solution;
(2) adding one-dimensional zinc oxide nano-rod into a solution containing bismuth salt and molybdenum salt, and preparing a visible light response three-dimensional composite material Bi through solvothermal reaction2MoO6/ZnO。
The invention discloses a method for preparing a three-dimensional composite material Bi responding to visible light by using water-soluble zinc salt, bismuth salt and molybdenum salt as raw materials2MoO6Application in ZnO.
Preferably, in the application, firstly, water-soluble zinc salt is used as a raw material, and a one-dimensional zinc oxide nanorod is prepared by a hydrothermal reaction in the presence of an alkali solution and a hydrazine monohydrate solution; then adding the one-dimensional zinc oxide nano-rod into a solution containing bismuth salt and molybdenum salt, and preparing the visible light response three-dimensional composite material Bi through solvothermal reaction2MoO6/ZnO。
The invention discloses a method for treating heavy metal wastewater by photocatalysis, which comprises the following steps:
(1) taking water-soluble zinc salt as a raw material, and preparing a one-dimensional zinc oxide nanorod by a hydrothermal reaction in the presence of an alkali liquor and a hydrazine monohydrate solution;
(2) adding one-dimensional zinc oxide nano-rod into the solution containing bismuth salt and molybdenum saltIn solution, preparing a three-dimensional composite material Bi responding to visible light through solvothermal reaction2MoO6/ZnO；
(3) Three-dimensional composite material Bi responding to visible light2MoO6Adding ZnO into the heavy metal wastewater, and illuminating to realize the photocatalytic treatment of the heavy metal wastewater.
In the invention, the water-soluble zinc salt is zinc sulfate heptahydrate, the bismuth salt is bismuth nitrate pentahydrate, the molybdenum salt is sodium molybdate dihydrate, and the alkali liquor is sodium hydroxide aqueous solution; in the solution of hydrazine monohydrate, the solvent is water.
In the invention, in the solution containing bismuth salt and molybdenum salt, the solvent is a mixed solvent of absolute ethyl alcohol and glycol, and the volume ratio of the absolute ethyl alcohol to the glycol is preferably (1-50): (1-10).
In the invention, in the step (1), the dosage ratio of the water-soluble zinc salt, the alkali liquor and the hydrazine monohydrate solution is 300-800 mg: 30-80 mL: 5-20 mL; the concentration of the alkali liquor is 0.25-0.75 mol/L; the mass concentration of the hydrazine monohydrate solution is 50 to 100 percent; the temperature of the hydrothermal reaction is 30-120 ℃, and the time is 2-8 h.
In the invention, in the step (2), the molar ratio of the bismuth salt to the molybdenum salt is (0.15-2.5) to (0.1-1.5); the temperature of the solvothermal reaction is 30-200 ℃, and the time is 12-48 h.
In the invention, in the step (2), the molar ratio of the one-dimensional zinc oxide nano-rod to the molybdenum salt is 1: 0.1-1.5; preferably 1 to (0.15-1.0).
In the invention, in the step (3), the illumination is xenon lamp light source illumination.
Visible light response three-dimensional composite material Bi in the invention2MoO6The preparation method of the/ZnO can be carried out as follows:
1. preparation of one-dimensional ZnO nano-rod
First, zinc sulfate heptahydrate (ZnSO) was added under stirring4·7H2O) is dissolved in aqueous sodium hydroxide (NaOH) solution, followed by addition of hydrazine monohydrate (N)2H4·H2O) an aqueous solution, and finally transferring the obtained solution to a reaction kettleHeating for reaction, and centrifugally washing the obtained white solid product to obtain a one-dimensional ZnO nanorod;
2. three-dimensional composite material Bi2MoO6Preparation of/ZnO
First, bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O) and sodium molybdate dihydrate (Na)2MoO4·2H2O) are respectively dissolved in ethylene glycol by ultrasonic wave, then the two are mixed together and stirred, and simultaneously ethanol is slowly added into the mixed solvent. And then adding the prepared ZnO nano-rod under the stirring condition and uniformly mixing. Finally transferring the obtained solution to a reaction kettle for heating reaction, and centrifugally washing the obtained gray yellow solid product to obtain three-dimensional Bi2MoO6A/ZnO composite material.
3. Photocatalytic degradation of heavy metal wastewater
The operation of photocatalytic degradation of heavy metal wastewater is specifically as follows, ZnO and Bi are explored under the same concentration2MoO6And a series of Bi2MoO6The degradation effect of ZnO (100 mg) on heavy metal ions in the wastewater.
The invention also discloses a visible light response three-dimensional composite material Bi prepared by the preparation method2MoO6/ZnO; and the three-dimensional composite material Bi2MoO6/ZnO, ZnO and Bi2MoO6The application in the treatment of heavy metal wastewater.
The invention has the advantages that:
1. the invention adopts a simple and easy-to-operate solvothermal method to prepare the three-dimensional Bi2MoO6the/ZnO composite photocatalyst has the advantages of simple preparation process and low raw material cost, is beneficial to reducing the preparation cost, and is easy to realize large-scale production.
2. Three-dimensional Bi of the invention2MoO6the/ZnO composite photocatalyst promotes Bi2MoO6And the separation efficiency of the photo-generated carriers in the ZnO nano particles effectively prolong the survival life of the photo-generated charges and promote the photocatalytic activity of the photo-generated charges; simultaneously, expensive metal elements in metal semiconductor materials are replaced, and the reduction is greatly realizedThe preparation cost is reduced.
3. Three-dimensional Bi obtained by the invention2MoO6the/ZnO nano composite material can improve the absorption and utilization of visible light and can effectively carry out photocatalytic degradation on the wastewater containing heavy metal ions.
Drawings
FIG. 1 shows ZnO and Bi2MoO6And Bi2MoO6Scanning Electron Microscopy (SEM) of/ZnO;
FIG. 2 shows ZnO and Bi2MoO6And Bi2MoO6The effect diagram of ZnO for treating heavy metal wastewater;
FIG. 3 shows Bi2MoO6The circulation effect diagram of the/ZnO composite material on the heavy metal wastewater.
Detailed Description
The present invention will be further described with reference to the following examples.
Example one
Preparing a one-dimensional ZnO nanorod: firstly, 600 mg of zinc sulfate heptahydrate is dissolved in 10 mL of sodium hydroxide aqueous solution (0.5 mol/L) under the condition of stirring, then 10 mL of hydrazine monohydrate aqueous solution (85 wt%, Cas 7803-57-8) is added, stirring is continued for 30 min, and finally the obtained solution is transferred to a reaction kettle and is heated to 90 ℃ for reaction for 5 h; and when the system is naturally cooled to room temperature, repeatedly washing the obtained white solid product with deionized water and ethanol for a plurality of times, and drying in an oven at the temperature of 60 ℃ to obtain the one-dimensional ZnO nanorod.
In order to observe the morphology of the material, a scanning electron microscope is used to characterize the product prepared in this example, and fig. 1 is a scanning electron microscope image of the one-dimensional ZnO nanorod prepared in this example, where (a) shows the one-dimensional ZnO nanorod prepared in this example.
Example two
Three-dimensional Bi2MoO6Preparation of/ZnO composite material: first, 0.33 mol of Bi (NO)3)3·5H2O and 0.16 mol of Na2MoO4·2H2O was dissolved in 5 mL of ethylene glycol by sonication. Then, the two are mixed together and stirredWhile slowly adding 30 mL of ethanol to the above mixed solvent for 5 min. Then adding the prepared 1 mol ZnO nano-rod under the stirring condition and mixing uniformly. Finally, transferring the obtained solution into a reaction kettle, heating to 160 ℃ and reacting for 24 hours. When the system is naturally cooled to room temperature, repeatedly washing the obtained gray yellow solid product with deionized water and ethanol for a plurality of times, and drying in an oven at the temperature of 80 ℃ to obtain the three-dimensional Bi2MoO6A/ZnO composite material.
In order to observe the morphology of the composite material, a scanning electron microscope is used to characterize the product prepared in this example, and fig. 1 shows a visible light response Bi prepared in this example2MoO6Scanning electron micrograph of/ZnO composite catalyst, (b) shows Bi prepared in this example2MoO6the/ZnO-0.16 (BZ-0.16) composite catalyst.
EXAMPLE III
Three-dimensional Bi2MoO6Preparation of/ZnO composite material: first, 0.65 mol of Bi (NO)3)3·5H2O and 0.33 mol of Na2MoO4·2H2O was dissolved in 5 mL of ethylene glycol by sonication. Then, both were mixed together and stirred for 5 min while 30 mL of ethanol was slowly added to the above mixed solvent. Then adding the prepared 1 mol ZnO nano-rod under the stirring condition and mixing uniformly. Finally, transferring the obtained solution into a reaction kettle, heating to 160 ℃ and reacting for 24 hours. When the belt system is naturally cooled to room temperature, repeatedly washing the obtained gray yellow solid product with deionized water and ethanol for a plurality of times, and drying in an oven at the temperature of 80 ℃ to obtain three-dimensional Bi2MoO6A/ZnO composite material.
In order to observe the morphology of the composite material, a scanning electron microscope is used to characterize the product prepared in this example, and fig. 1 shows a visible light response Bi prepared in this example2MoO6Scanning electron micrograph of/ZnO composite catalyst, (c) shows Bi prepared in this example2MoO6the/ZnO-0.33 (BZ-0.33) composite catalyst.
Example four
Three-dimensional Bi2MoO6Preparation of/ZnO composite material: first, 1.3 mol of Bi (NO)3)3·5H2O and 0.65 mol of Na2MoO4·2H2O was dissolved in 5 mL of ethylene glycol by sonication. Then, both were mixed together and stirred for 5 min while 30 mL of ethanol was slowly added to the above mixed solvent. Then adding the prepared 1 mol ZnO nano-rod under the stirring condition and mixing uniformly. Finally, transferring the obtained solution into a reaction kettle, heating to 160 ℃ and reacting for 24 hours. When the belt system is naturally cooled to room temperature, repeatedly washing the obtained gray yellow solid product with deionized water and ethanol for a plurality of times, and drying in an oven at the temperature of 80 ℃ to obtain three-dimensional Bi2MoO6the/ZnO-0.65 composite material.
In order to observe the morphology of the composite material, a scanning electron microscope is used to characterize the product prepared in this example, and fig. 1 shows a visible light response Bi prepared in this example2MoO6Scanning electron micrograph of/ZnO composite catalyst, (d) shows Bi prepared in this example2MoO6the/ZnO-0.65 (BZ-0.65) composite catalyst.
EXAMPLE five
Three-dimensional Bi2MoO6Preparation of/ZnO composite material: first, 1.95 mol of Bi (NO)3)3·5H2O and 0.98 mol of Na2MoO4·2H2O was dissolved in 5 mL of ethylene glycol by sonication. Then, both were mixed together and stirred for 5 min while 30 mL of ethanol was slowly added to the above mixed solvent. Then adding the prepared 1 mol ZnO nano-rod under the stirring condition and mixing uniformly. Finally, transferring the obtained solution into a reaction kettle, heating to 160 ℃ and reacting for 24 hours. When the belt system is naturally cooled to room temperature, repeatedly washing the obtained gray yellow solid product with deionized water and ethanol for a plurality of times, and drying in an oven at the temperature of 80 ℃ to obtain three-dimensional Bi2MoO6A/ZnO composite material.
In order to observe the morphology of the compounded material, a scanning electron microscope is used to characterize the product prepared in the embodiment, and fig. 1 shows the product prepared in the embodimentPrepared visible light response Bi2MoO6Scanning electron micrograph of/ZnO composite catalyst, (e) shows Bi prepared in this example2MoO6the/ZnO-0.98 (BZ-0.98) composite catalyst.
EXAMPLE six
Flower-like Bi2MoO6Preparation of the material: first, 1.3 mol of Bi (NO)3)3·5H2O and 0.65 mol of Na2MoO4·2H2O was dissolved in 5 mL of ethylene glycol by sonication. Then, both were mixed together and stirred for 5 min while 30 mL of ethanol was slowly added to the above mixed solvent. Finally, transferring the obtained solution into a reaction kettle, heating to 160 ℃ and reacting for 24 hours. When the belt system is naturally cooled to room temperature, repeatedly washing the obtained gray yellow solid product with deionized water and ethanol for a plurality of times, and drying in an oven at the temperature of 80 ℃ to obtain flower-shaped Bi2MoO6A material.
In order to observe the morphology of the material, the product prepared in this example was characterized by scanning electron microscopy, and fig. 1 shows the flower-like Bi prepared in this example2MoO6Scanning Electron micrograph of catalyst, (f) shows flower-like Bi prepared in this example2MoO6A catalyst.
Based on the above, it can be seen from the attached fig. 1 (a) that the prepared ZnO has a one-dimensional rod-like morphology, a diameter of 300-400 nm, and a length of several microns. From FIGS. 1 (b), (c), (d) and (e), it was found that Bi supported on ZnO nanorods was supported with increasing contents of bismuth source and molybdenum source of the reaction precursors2MoO6Gradually converts the granular morphology into a two-dimensional nanosheet morphology, and when the content of the bismuth source and the molybdenum source is too large, flower-shaped Bi is formed2MoO6Agglomerated on the ZnO nano-rod. FIG. f shows Bi in the form of flower balls2MoO6Is composed of a large amount of Bi2MoO6The nano sheets are combined.
EXAMPLE seven
The method for treating the heavy metal wastewater through photocatalysis comprises the following specific steps: ZnO and Bi are mixed2MoO6And a series of products Bi2MoO6the/ZnO (100 mg each) was added to 50 mg/L of the heavy metal wastewater (hexavalent chromium) solution. Each group of samples was stirred for one hour in the dark to achieve adsorption-desorption equilibrium. After equilibration, the mixture was placed under stirring in a xenon lamp light source (300W, lambda)>400 nm) for 150 min. And finally, analyzing and comparing the degradation effect by a UV-vis spectrophotometry after the xenon lamp irradiation.
FIG. 2 shows ZnO and Bi2MoO6And Bi2MoO6Effect diagram of/ZnO treatment of heavy metal wastewater, and Bi is found through the effect diagram2MoO6The catalytic efficiency of ZnO- (0.16-0.98) to heavy metal wastewater in the solution is obviously superior to that of ZnO and Bi2MoO6. If the water-soluble zinc salt, bismuth salt and molybdenum salt are directly subjected to one-pot solvothermal reaction (under the conditions of the example II), the removal rate of the obtained catalyst is about 45 percent in 150 hours.
Example eight
Bi2MoO6The cyclicity of ZnO to heavy metal wastewater degradation comprises the following steps: to study Bi2MoO6The recycling performance of ZnO in heavy metal wastewater treatment is realized by optimizing 100 mg of Bi with the best degradation effect2MoO6the/ZnO-0.65 (three cycles) was added to a heavy metal ion solution (50 mg/L, 50 mL) and irradiated with visible light for 150 min with stirring. After the reaction is finished, the content of the heavy metal wastewater in the solution is analyzed and determined by using a UV-vis spectrophotometry.
FIG. 3 shows Bi2MoO6The circulation effect diagram of the/ZnO heavy metal wastewater shows that 50 mg/L heavy metal ions can be completely degraded within 150 min after three times of circulation. The second and third cycle degradation effects are reduced compared with the first cycle degradation effect, but the degradation capability of heavy metal ions still shows good degradation effect. Therefore, the catalyst can be repeatedly used and has good stability.
To summarize:
through the analysis, the invention uses the simple and easy-to-operate solvothermal method to react Bi with Bi2MoO6Is modified on a one-dimensional ZnO nano rod to successfully prepare three-dimensional Bi2MoO6a/ZnO nano composite material. The composite material disclosed by the invention has stronger visible light photocatalytic degradation on heavy metal wastewater, and can almost reach 100% removal rate. In addition, the invention has the advantages of simple manufacturing process, economy, environmental protection and the like, and the preparation cost is low, so the invention has good application prospect in wastewater treatment.
Claims (5)
1. Visible light response three-dimensional composite material Bi2MoO6The application of the/ZnO in the heavy metal wastewater treatment is characterized in that the visible light response three-dimensional composite material Bi2MoO6The preparation method of the ZnO comprises the following steps:
(1) taking water-soluble zinc salt as a raw material, and preparing a one-dimensional zinc oxide nanorod by a hydrothermal reaction in the presence of an alkali liquor and a hydrazine monohydrate solution; the dosage ratio of the water-soluble zinc salt, the alkali liquor and the hydrazine monohydrate solution is 300-800 mg: 10 mL: 5-20 mL; the concentration of the alkali liquor is 0.5 mol/L; the mass concentration of the hydrazine monohydrate solution is 50 to 100 percent;
(2) adding one-dimensional zinc oxide nano-rod into a solution containing bismuth salt and molybdenum salt, and preparing a visible light response three-dimensional composite material Bi through solvothermal reaction2MoO6/ZnO; the molar ratio of the one-dimensional zinc oxide nano-rod to the molybdenum salt is 1: 0.1-1.5.
2. The use of claim 1, wherein the water soluble zinc salt is zinc sulfate heptahydrate, the bismuth salt is bismuth nitrate pentahydrate, the molybdenum salt is sodium molybdate dihydrate, and the alkaline solution is aqueous sodium hydroxide solution; in a hydrazine monohydrate solution, the solvent is water; in the solution containing bismuth salt and molybdenum salt, the solvent is a mixed solvent of absolute ethyl alcohol and glycol.
3. The use of claim 2, wherein the volume ratio of the absolute ethanol to the glycol is (1-50) to (1-10).
4. The use according to claim 1, wherein in the step (1), the temperature of the hydrothermal reaction is 30-120 ℃ and the time is 2-8 h; in the step (2), the molar ratio of the bismuth salt to the molybdenum salt is (0.15-2.5) to (0.1-1.5); the temperature of the solvothermal reaction is 30-200 ℃, and the time is 12-48 h.
5. Use according to claim 1, characterized in that the heavy metal is hexavalent chromium.
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